CN106025173A - Sea cell Mg-Li-Zn alloy electrode modified by yttrium-rich mischmetal element and preparing method - Google Patents

Sea cell Mg-Li-Zn alloy electrode modified by yttrium-rich mischmetal element and preparing method Download PDF

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Publication number
CN106025173A
CN106025173A CN201610312263.5A CN201610312263A CN106025173A CN 106025173 A CN106025173 A CN 106025173A CN 201610312263 A CN201610312263 A CN 201610312263A CN 106025173 A CN106025173 A CN 106025173A
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alloy
alloy electrode
magnesium
vacuum
rare earth
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徐强
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Tianjin University
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Tianjin University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • H01M4/08—Processes of manufacture
    • H01M4/12—Processes of manufacture of consumable metal or alloy electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/466—Magnesium based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/30—Deferred-action cells
    • H01M6/32—Deferred-action cells activated through external addition of electrolyte or of electrolyte components
    • H01M6/34—Immersion cells, e.g. sea-water cells

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a sea cell Mg-Li-Zn alloy electrode modified by yttrium-rich mischmetal element and a preparing method. The alloy electrode is prepared from 80-90% of Mg, 5-15% of Li, 0.5-2.5% of Zn and 0.2-3% of RE. The yttrium-rich mischmetal element and metal zinc are added into Mg-Li-based alloy through a vacuum melting technology, the multi-element Mg-Li-Zn-RE alloy electrode is prepared, and discharging current density and corrosion resistance of the Mg-Li-Zn-RE alloy electrode are improved. The corrosion potential is larger than 1.45 V (vs.SCE) in a 3.5% sodium chloride water solution, the discharging current density is larger than 40 mA/ cm<2> under the voltage of 1.0 V (vs.SCE), the discharging performance is obviously higher than that of a traditional Mg-Li-based alloy electrode, corrosion resistance is improved, the service life is prolonged, and a high-performance anode material of a sea cell is formed.

Description

Utilize rich yttrium mixed rare earth element modified seawater battery Mg-Li-Zn alloy electrode and preparation method
Technical field
The invention belongs to seawater battery technical field, particularly relate to utilize the rich element modified seawater battery of yttrium mixed rare earth Mg-Li-Zn alloy electrode and preparation method.
Background technology
Along with the fast development of coast defence construction, marine resources development and marine ecology research, countries in the world are under marine environment The demand of the high performance chemical electric power source of work increases the most day by day.Magnesium metal has that electrode potential is negative, theoretical specific capacity is big (2205Ah·kg-1), high (the 6.8kWh kg of specific energy-1), the advantage such as cheap, environmentally friendly, there is excellence Discharge performance, it has also become a kind of important electrochemical anode material.Using magnesium and magnesium alloy as anode all kinds of magnesium cells (as Magnesium-sea-water activated battery, magnesium-hydrogen peroxide semi-fuel battery and magnesium-seawater dissolved oxygen semi-fuel cell) there is energy density High, electric discharge steadily, storage time length, the feature such as safe and reliable and cheap, have become as one, current marine energy field The focus received much concern.
In recent years, a kind of novel Mg-Li base alloy starts to be paid close attention to by people, just as the anode material of seawater battery Becoming one, marine energy field study hotspot.Lithium metal (Li) is the most active anode material.Its equilibrium potential ratio Mg is more negative, its electrochemical equivalent (3.86Ah g-1) and theoretical specific energy (13.0kWh kg-1) it is above metal Mg, Li Yu Mg is formed Mg-Li base alloy, by means of high electric discharge activity and the high-energy-density of Li, magnesium sun can be improved The electric discharge activity of pole, reduces " hysteresis effect ", improves the specific energy of Magnesium sea water battery.
Rare earth element, owing to having the extranuclear strucure of uniqueness, has a wide range of applications at metallurgical, Material Field.As only Change metal bath, refining alloy tissue, improve material mechanical performance and decay resistance etc., have been widely used for magnesium and close The modification of gold, wherein rare earth element yttrium (Y) is applied the most extensive.But expensive due to pure rare earth element, thus Limit rare earth element application in magnesium alloy electrode.In order to improve the discharge performance of Mg-Li base alloy further, this Invent and richness yttrium mixed rare earth (RE) and metallic zinc (Zn) element are joined the conjunction of Mg-Li base simultaneously as alloying element Jin Zhong, devises a kind of polynary Mg-Li-Zn-RE alloy, as the high performance anode material of seawater battery.
Summary of the invention
In order to improve discharge current and the technological approaches of discharging efficiency of Mg-Li base alloy electrode simultaneously；Improve further The discharge performance of Mg-Li base alloy, the discharge current density of solution seawater battery Mg-Li base alloy electrode is little and uses the longevity Ordering short problem, richness yttrium mixed rare earth (RE) and metallic zinc (Zn) element are added by the present invention simultaneously as alloying element Enter in Mg-Li base alloy, it is proposed that a kind of polynary Mg-Li-Zn-RE alloy, become the high performance anode of seawater battery Material.
Technical scheme is as follows:
A kind of polynary Mg-Li--Al-RE alloy electrode, composition and the weight/mass percentage composition of its alloy electrode are as follows:
Mg:80-90%；
Li:5-15%；
Zn:0.5-2.5%；
RE:0.2-3%.
Described rich yttrium mixed rare earth element (RE) purity is 98%-99%, containing Ce:45%-51%, La:23%-28%, Pr:5%-7%, Nd:12%-17%, nonmetallic inclusion content < 1%.
The preparation method of the polynary Mg-Li--Zn-RE alloy electrode of the present invention, its step is as follows:
1) in vacuum melting furnace, first crucible is preheated to kermesinus, adds the pure magnesium ingot through drying, start to be passed through SF6 + Ar mixed gas；
2) at SF6Under+Ar gas shield, it is continuously heating to 700～720 DEG C, adds pure zinc ingot；
3) it is warmed up to when 780～810 DEG C add magnesium-richness yttrium mixed rare earth (Mg-RE) intermediate alloy, treats whole raw material After fusing, stir；
4), after alloy melting is good, magnesium oxide and the coverture mixture of surface efflorescence is removed, 780～810 DEG C of standings More than 30min, then pours into a mould；
5), after cast, gained alloy sample is incubated 10h in vacuum heat treatment furnace at a temperature of 300 DEG C；Obtain Mg-Li--Zn-RE alloy electrode.
Described vacuum melting furnace is vacuum resistance smelting furnace or vacuum induction melting furnace.
Due to the density difference great disparity of rare earth element with magnesium metal, the fusing point of most of rare earth elements is higher than the fusing point of magnesium, and two Person be difficult at a lower temperature Direct Uniform consolute and do not produce component segregation.In order to solve this problem, this patent uses Mischmetal magnesium intermediate alloy (Mg-RE alloy) is as the addition carrier of rich yttrium mixed rare earth element, to eliminate magnesium alloy Component segregation, make the even tissue of Mg-Li base alloy.
The present invention has the advantage that and good effect:
1. contain the corrosion in 3.5% sodium-chloride water solution of the polynary Mg-Li--Zn-RE alloy electrode of rich yttrium mixed rare earth element Current potential is more than-1.45V (vs.SCE), and under-1.0V voltage, (vs.SCE) discharge current density is more than 40mA/cm2, Discharge performance, apparently higher than traditional Mg-Li base alloy electrode, not only increases discharge current density, also improves it anti-corrosion Performance and used life.
2., relative to the element modified technology of pure rare earth, use mixed rare-earth elements to be modified, reduce Mg-Li-Zn base electrode Preparation cost.
Accompanying drawing explanation
The microscopic structure (chemical polishing) of Fig. 1 (a) low range polynary Mg-11.9Li-1.5Zn-1.6RE alloy electrode sample
The microscopic structure (chemical polishing) of Fig. 1 (b) high magnification polynary Mg-11.9Li-1.5Zn-1.6RE alloy electrode sample
Detailed description of the invention
More than 1 yuan of Mg-15Li-2.5Zn-2.5RE alloy electrode of embodiment
This alloying component (mass fraction) is: Mg:80%, Li:15%, Zn:2.5%, RE:2.5%.
The preparation process of this alloy electrode: in vacuum melting furnace, is first preheated to kermesinus by crucible, adds through overbaking Dry pure magnesium ingot, starts to be passed through SF6+ Ar mixed gas；At SF6Under+Ar gas shield, it is continuously heating to 700 DEG C, Add pure zinc ingot；It is warmed up to when 780 DEG C add magnesium-richness yttrium mixed rare earth (Mg-RE) intermediate alloy, treats whole raw material After fusing, stir；After alloy melting is good, remove magnesium oxide and the coverture mixture of surface efflorescence, at 780 DEG C Stand more than 30min, then pour into a mould；After cast, gained alloy sample in vacuum heat treatment furnace at a temperature of 300 DEG C Insulation 10h；Obtain polynary Mg-15Li-2.5Zn-2.5RE alloy electrode.
This alloy electrode discharge performance in 3.5%NaCl solution: corrosion potential is-1.51V (vs.SCE), permanent Pressure discharge current density is 45.8mA/cm2(-1.0V vs.SCE)。
More than 2 yuan of Mg-11.9Li-1.5Zn-1.6RE alloy electrode of embodiment
This alloying component (mass fraction) is: Mg:85%, Li:11.9%, Zn:1.5%, RE:1.6%.
The preparation process of this alloy electrode: in vacuum melting furnace, is first preheated to kermesinus by crucible, adds through overbaking Dry pure magnesium ingot, starts to be passed through SF6+ Ar mixed gas；At SF6Under+Ar gas shield, it is continuously heating to 710 DEG C, Add pure zinc ingot；It is warmed up to when 790 DEG C add magnesium-richness yttrium mixed rare earth (Mg-RE) intermediate alloy, treats whole raw material After fusing, stir；After alloy melting is good, remove magnesium oxide and the coverture mixture of surface efflorescence, at 790 DEG C Stand more than 30min, then pour into a mould；After cast, gained alloy sample in vacuum heat treatment furnace at a temperature of 300 DEG C Insulation 10h；Obtain polynary 80Mg-15Li-2.5Zn-2.5RE alloy electrode.
This alloy electrode chemical property in 3.5%NaCl solution: corrosion potential is-1.46V (vs.SCE), Constant voltage discharge electric current density is 44.5mA/cm2(-1.0V vs.SCE)。
More than 3 yuan of 90Mg-5Li-0.2Zn-3RE alloy electrode of embodiment
This alloying component (mass fraction) is: Mg:90%, Li:9.3%, Zn:0.5%, RE:0.2%.
The preparation process of this alloy electrode: in vacuum melting furnace, is first preheated to kermesinus by crucible, adds through overbaking Dry pure magnesium ingot, starts to be passed through SF6+ Ar mixed gas；At SF6Under+Ar gas shield, it is continuously heating to 715 DEG C, Add pure zinc ingot；It is warmed up to when 800 DEG C add magnesium-richness yttrium mixed rare earth (Mg-RE) intermediate alloy, treats whole raw material After fusing, stir；After alloy melting is good, remove magnesium oxide and the coverture mixture of surface efflorescence, at 800 DEG C Stand more than 30min, then pour into a mould；After cast, gained alloy sample in vacuum heat treatment furnace at a temperature of 300 DEG C Insulation 10h；Obtain polynary 90Mg-9.3Li-0.5Zn-0.2RE alloy electrode.
This alloy electrode chemical property in 3.5%NaCl solution: corrosion potential is-1.44V (vs.SCE), Constant voltage discharge electric current density is 42.6mA/cm2(-1.0V vs.SCE)。
More than 4 yuan of Mg-10Li-1.5Zn-0.2RE alloy electrode of embodiment
This alloying component (mass fraction) is: Mg:88.3%, Li:10%, Zn:1.5%, RE:0.2%.
The preparation process of this alloy electrode: in vacuum melting furnace, is first preheated to kermesinus by crucible, adds through overbaking Dry pure magnesium ingot, starts to be passed through SF6+ Ar mixed gas；At SF6Under+Ar gas shield, it is continuously heating to 720 DEG C, Add pure zinc ingot；It is warmed up to when 810 DEG C add magnesium-richness yttrium mixed rare earth (Mg-RE) intermediate alloy, treats whole raw material After fusing, stir；After alloy melting is good, remove magnesium oxide and the coverture mixture of surface efflorescence, at 810 DEG C Stand more than 30min, then pour into a mould；After cast, gained alloy sample in vacuum heat treatment furnace at a temperature of 300 DEG C Insulation 10h；Obtain polynary Mg-10Li-0.5Zn-0.2RE alloy electrode.
This alloy electrode chemical property in 3.5%NaCl solution: corrosion potential is-1.42V (vs.SCE), Constant voltage discharge electric current density is 41.4mA/cm2(-1.0V vs.SCE)。
The present invention is open and the utilization richness yttrium mixed rare earth element modified seawater battery Mg-Li-Zn alloy electrode that proposes and system Preparation Method, those skilled in the art can suitably change the links such as condition route realize by using for reference present disclosure, although this Alloy electrode composition and the technology of preparing of invention are described by preferred embodiment, the obvious energy of person skilled In without departing from present invention, spirit and scope, material described herein composition and technology path are modified or again Combination, realizes final alloy electrode.Special needs to be pointed out is, all similar replacements and change are to this area Being apparent from for technical staff, they are considered as being included in present invention spirit, scope and content.

Claims (4)

1. a polynary Mg-Li--Zn-RE alloy electrode, is characterized in that the composition of alloy electrode and weight/mass percentage composition are as follows:
Mg:80-90%；
Li:5-15%；
Zn:0.5-2.5%；
Rich yttrium mixed rare earth element: 0.1-3%.
2. alloy electrode as claimed in claim 1, is characterized in that described rich yttrium mixed rare earth elemental purity is 98%-99%, containing Ce: 45%-51%, La:23%-28%, Pr:5%-7%, Nd:12%-17%, nonmetallic inclusion content < 1%.
3. the preparation method of many yuan of Mg-Li--Zn-RE alloy electrodes of claim 1, is characterized in that
1) in vacuum melting furnace, first crucible is preheated to kermesinus, adds the pure magnesium ingot through drying, start to be passed through SF6 + Ar mixed gas；
2) at SF6Under+Ar gas shield, it is continuously heating to 700～720 DEG C, adds pure zinc ingot；
3) it is warmed up to when 780～810 DEG C add magnesium-mischmetal (Mg-RE) intermediate alloy, after whole melting sources, stirs Mix uniformly；
4), after alloy melting is good, remove the magnesium oxide of surface efflorescence and coverture mixture, 780～810 DEG C stand 30min with On, then pour into a mould；
5), after cast, gained alloy sample is incubated 10h in vacuum heat treatment furnace at a temperature of 300 DEG C；Obtain Mg-Li-Zn-RE Alloy electrode.
4. method as claimed in claim 3, is characterized in that described vacuum melting furnace is vacuum resistance smelting furnace or vacuum induction melting Stove.
CN201610312263.5A 2016-05-11 2016-05-11 Sea cell Mg-Li-Zn alloy electrode modified by yttrium-rich mischmetal element and preparing method Pending CN106025173A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040241036A1 (en) * 2001-06-11 2004-12-02 Andrea Meyer-Lindenberg Medical implant for the human or animal body

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040241036A1 (en) * 2001-06-11 2004-12-02 Andrea Meyer-Lindenberg Medical implant for the human or animal body

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
林亚青，等: ""镁海水电池及镁阳极材料的研究进展"", 《材料保护》 *
王学新: ""Mg，Mg-Li，Mg-Li-Al-Y 和 Mg-Li-Al-Zn 合金的电化学性能的研究"", 《中国优秀硕士学位论文全文数据库》 *

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